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By Hiromichi Ohta

Precise thermal properties of molten materials are essentially required for analyzing the metal production process. These properties are also important as a clue to consider the dynamic structure of liquid materials. However, it is difficult to obtain the precise thermal diffusivity values of molten oxides at high temperature because of the experimental uncertainties arising from the bubble formation or the severe separation of radiative and conductive heat components. Recently a novel laser flash method has also developed for measuring thermal diffusivity of molten oxides at high temperature. In this new technique, the sample is melted in a metal crucible and heated to the desired temperature. A single laser pulse is flashed on the bottom of the metal crucible and the infrared ray irradiated from the same bottom surface is measured for obtaining the temperature decay, from which the thermal diffusivity of the liquid sample can be estimated. The usefulness and validity of this new laser flash technique have been confirmed by obtaining the thermal diffusivity values of silicate melts in the wide temperature range between 773 and 1673 K.

Jan 1, 2003

By Milorad Cirkovic

Kinetics of copper concentrate oxidation in roasting processes in a fluidized bed reactor has been studied at temperatures between 600°C and 720°C using particles of 0.038 to 2.5 mm in average size. The analysis of composition of samples has been done by chemical methods. Phase composition has been determined by Siemens X-ray equipment with Cu anticathode and Ni filters at a voltage of 40 kV and a current of 18 mA. The content of sulphur has decreased from 33.23 to 19.02 mass percent with the increase of temperature, but the content of Fe304 has increased from 0.15 to 17.14 mass percent. The new mechanism of copper concentrate oxidation in a fluidized bed reactor is proposed in this study. It has been shown from the mathematical model that the velocity of oxidation of copper concentrate between 600°C and 720°C is virtually controlled by the rate of diffusion of 02 through the layer of reaction product.

Jan 1, 1999

By David R. Brosnahan

Increased Cu grades due to chalcopyrite-rich ore from The Doe Run Company's new Casteel Mine prompted a program to increase Cu recovery. Preliminary tests indicated that prohibitive quantities of FeS2 float with chalcopyrite. Point counting of mill stream samples showed that locking was not a major problem, although grinding to finer particle size enhanced the floatability of both chalcopyrite and marcasite. Backscattered electron images and microprobe analyses of FeSz minerals revealed the presence of Pb which appears to occur as solid solution in marcasite, and as a sub-micron particulate Pb phase in pyrite.

Jan 1, 1987

By J. R. Goode

There are at least a dozen methods of selectively removing cerium from a mixture of the rare earth elements (REE) including separation techniques based on the oxidation of cerium to the quadrivalent state. Several of the oxidation processes have been operated on a commercial scale, others have been tested and in some cases are part of proposed flowsheets. In this paper, we describe and compare the various methods. We also present preliminary estimates of the costs of early Ce removal and discuss recovery and purity aspects of the options.

By Satoshi Itoh

Phase equilibria and activities of the components in the liquid lead-antimony-oxygen temary system, which is of fundamental importance for discussing the recovery of lead and antimony from a used lead-battery, have been investigated at 1173 and 1223 K. The two liquid phases of metal and oxide were observed at the temperatures studied, and the tie lines indicating isoactivities were determined. The activities of PbO, Sb015 and Sb203 in the PbO-SbOu and PbO-Sb203 pseudo-binary systems were then obtained by applying the Gibbs-Duhem equation to the phase relation of metal-oxide equilibrium. Both in the pseudo-binary systems the activities exhibit negative deviations from Raoult's law. The vapor pressures of lead, antimony and lead oxide, antimony oxide were calculated by using the activities of the components in the lead-antimony-oxygen ternary system. As a result, an oxidation of antimony concentrated in an anode slime followed by evaporation as antimony oxide Sb406 was found to be considerably effective for the recovery of lead and antimony from a used lead-battery.

Jan 1, 2003

By Eoghan T. M Doyle

Oxide mixtures of nickel (NiO), cobalt (COO) and chromium (Cr203) were prepared with graphite in stoichiometric amounts and the powder mixtures were compacted to produce cylindrical pellets. The composition of chromium oxide in these mixtures were varied. Pressed pellets were reduced in a flowing stream of argon-4% hydrogen gas (500 ml/min). Both slow and rapid heating methods were adopted to raise the temperature of a pellet during reduction of oxides to form superalloy powder. The reduction temperature was varied between. 1523 and 1623K. The effect of heating rate and niobium oxide addition on the microstructure of the superalloy produced was studied by using ordinary light and scanning electron microscopes. New phases formed as a result of reduction were identified by X-ray powder diffraction technique. The mechanism of reduction of oxides together with the microstructure of NiCrCo alloy are discussed. The thermodynamics of formation of ternary alloy phase is elucidated on the basis of binary phase equilibria and Gibbs free energy of mixing data for the constituent alloy compositions.

Jan 1, 1992

By G. A. Brooks

Reactive ball milling has been proposed as a new route for producing carbides from oxides through carbothermic reduction. It is claimed that through milling oxide and graphite powders to the nanoscale, amorphous materials with very high reactivity are formed, that allows for easy transformation of the starting material to another in a subsequent thermal process. Thermodynamic analysis of this proposed process suggests that unless particle sizes are reduced to below 10nm, then reduction in size alone cannot explain a change in the stability of oxides. Even with nanometer scale powders, the products formed need to have a lower total surface energy than the reactants before a chemical change will occur. A model developed by Bhattacharya and Arzt for predicting localized temperature changes based on milling conditions suggest that temperature rises less than 400 K will be achieved in laboratory conditions. The present calculations suggest that nanometer scale powders formed through high speed ball milling (> I 0 mls) may have undergone a process analogous to melting and quenching. Further work is required to fully distinguish these features.

Jan 1, 2003

By G. A. Brooks

Reactive ball milling has been proposed as a new route for producing carbides from oxides through carbothcrmic reduction. It is claimed that through milling oxide and graphite powders to the nanoscale, amorphous materials with very high reactivity are formed, that allows for easy transformation of the starting material to another in a subsequent thermal process. Thermodynamic analysis of this proposed process suggests that unless particle sizes are reduced to below 10nm, then reduction in size alone cannot explain a change in the stability of oxides. Even with nanometer scale powders, the products formed need to have a lower total surface energy than the reactants before a chemical change will occur. A model developed by Bhattacharya and Arzt for predicting localized temperature changes based on milling conditions suggest that temperarure rises less than 400 K will be achieved in laboratory conditions. The present calculations suggest that nanometer scale powders formed through high speed ball milling (>10 mls) may have undergone a process analogous to melting and quenching. Further work is required to fully distinguish these features.

Jan 1, 2003

By Moo Eob Choi

A new process for converting sulfur dioxide to elemental sulfur by a cyclic process involving calcium sulfide and calcium sulfate without generating secondary pollutants was developed at the University of Utah. In this process, sulfur dioxide is reacted with calcium sulfide to produce elemental sulfur and calcium sulfate. The latter is reduced by hydrogen to regenerate calcium sulfide. In the present work, the effects of different pelletization conditions for the initial reactant calcium sulfate on the strength and reactivity of the pellets were determined. These conditions include the type, amount, and impregnation method of catalyst, binder amount, and sintering. Experiments were also performed to determine the effects of temperature in the range of 973-1173 K, pellet size, cycle repetition, and water vapor or carbon dioxide content in sulfur dioxide stream on the reaction rates of the cyclic process. Nickel-catalyzed fired pellets produced by the use of molasses or cement as a binder showed good reactivity as well as high compressive strength during the cyclic tests. The binder amount did not significantly affect the reaction rate.

Jan 1, 2006

By Kazuki Morita

Dissolution mechanism and solubility of chlorine in the oxide melts, such as CaO-SiO2-Al2O3 (-Na2O), Na2O-SiO2-Al2O3 and CaO-SiO2-FeO systems, have been equilibrium technique was employed with controlled Po2 and PCl2, (Po2 = 10-6 -10 19 atm, PCl2 10-6 -10-13 atm at 1673-1748 K). The solubility of chlorine in the 40mass%CaO-40mass%SiO2- 20mass%Al2O3, slag was found to vary in proportion to Pb2/ w and pc/z/p' which proved that chlorine dissolved in the melts as C1 anion. Hence, the chloride capacity (CCI-), indicating the ability of molten oxide to absorb chlorine, has been defined as; The Ccl value was observed to increase with increasing slag basicity and temperature, and showed a reasonable relationship with that Of CS2-. Based on the result obtained in the present study, chlorine distribution during incineration with slags was predicted quantitatively.

Jan 1, 2003

By Zhigang Zak Fang, Michael L. Free, Jaehun Cho, Syamantak Roy, Amarchand Sathyapalan

Leaching characteristics of impurity removal from the Upgraded Titania Slag (UGS) using hydrochloric and boric acids has been investigated. Specifically, this study has focused on removal of iron oxides from the UGS that has been reduced by hydrogen gas and magnesium at 750oC for 5 hours. Reduced UGS is mainly composed of titanium hydride and impurities like iron oxides, silicon oxide, aluminum oxide, and magnesium oxide. The concentration of hydrochloric and boric acids and the leaching temperature have been chosen as the prime variables to identify the optimum conditions and leaching characteristics for removal of iron oxides. It was observed that under the constraint that 1 wt % of titanium hydride loss is the maximum amount tolerable, 0.1M HCl with 1M boric acid and 90oC are the most effective parameters for iron removal from the reduced UGS. Also, the overall rate of reaction seems to follow interfacial reaction controlled kinetics. The calculated activation energy of the reaction is 73.90kJ/mol.

Jan 1, 2016

By V. Jiricny

The novel spouted-bed electrode (SBE) is a cathode system where copper is deposited at a high current density in a moving bed of copper particles. Preliminary results on the deposition of copper from acidic sulfate electrolytes using this novel cathode system were described during Copper '95 conference. Despite a high current density, the electrical energy consumption was equal to or lower than that in the conventional electrowinning. The present paper describes more investigations on SBE. The SBE consists of copper particles with approximately 1 mm diameter onto which copper is deposited from acidic sulfate electrolyte whose composition is similar to conventional electrowinning. Three types of anodes were used in conjunction with the spouted-bed cathode, namely, DSA anode for oxygen evolution, and two novel anodes. One anode is less expensive than DSA; however it showed much promise in energy consumption. At a superficial current density of 2200 A/m2, the energy consumption was around 1.0 kWh/kg copper. The research activities described in this paper were supported by BHP Copper.

Jan 1, 1999

By V. L. Stolyarova

As part of an effort to develop the fluoride electrolysis route for the production of rare earth metals and alloys, a study of the thermodynamic properties of DyF3 has been carried out by Knudsen cell mass spectrometry. A quadrupole mass spectrometer QMS 420 was used in conjunction with the Knudsen cell arrangement. The experiments were carried out in the temperature range 1280-1440 K. Vaporization was carried out from platinum, molybdenum and tantalum cells. The Dy*, DyF+, DyF2+ fragment ions and the DyF3 parent ion were identified in the mass spectrum of the DyF3 vapour. The DyF, vapour pressure was obtained by the complete isothermal vaporizadon method as well as the ion current comparison method, and the enthalpy of sublimation of DyF3 was evaluated. From the DyF3 vapour pressure data obtained at different temperatures, the enthalpies of formation of DyF3 in the gaseous as well as condensed phases have been evaluated. The experimental data are compared with the thermodynamic information available in literature.

Jan 1, 1995

By Toshiyuki Nohira, Eiichi Takeuchi, Tetsuo Oishi, Hideki Ono, Hirokazu Konishi

The Dy-Nd-Pr-Ni alloy sample was prepared by cathodic potentiostatic electrolysis at 0.65 V (vs. Li+/Li) for 1 h using a Ni plate in a molten LiCl-KCl-DyCl3-NdCl3-PrCl3 system at 723 K. The highest mass ratio (Dy/Nd+Pr) in the alloy sample was observed to be 50 at 0.65 V. Anodic potentiostatic electrolysis at 2.20 V for 12 h was conducted using the Nd-Fe-B magnet electrode in a molten LiCl-KCl system. All elements were almost dissolved from the magnet, and the original form of the magnet disintegrated. After anodic potentiostatic electrolysis at 2.20 V, cathodic potentiostatic electrolysis was conducted at 1.00 V for 5 h using a Mo plate in order to remove the dissolved Fe from the bath. Finally, cathodic potentiostatic electrolysis was conducted at 0.65 V for 12 h using a Ni plate. The mass ratio of Dy/Nd in the alloy sample was determined to be about 18.

Jan 1, 2015

By Katsunori Yamaguchi

The zinc, lead and alumina contents in copper smelting slag are increasing with the increase in waste recycling. The recovery of base metals such as lead and zinc from copper converter slag is important from both an economical and environmental perspective. As a fundamental study of the metal recovery by reduction process, activity coefficients of ZnO and PbO in the CaO-SiO2-FeOx-5mass%AlO1.5 slag under iron saturation at 1573K are derived from the data of slag-metal equilibrium experiments. On the basis of the obtained data, the activity coefficients of ZnO and PbO in the CaO-SiO2-FeOx-5mass%AlO1.5 slag were compared with those of the CaO-SiO2-FeOx ternary system. Addition of alumina increases activities coefficient of ZnO and PbO in SiO2 rich side of the slag, and decreases them in CaO rich side.

Jan 1, 2006

By Stuart D. Miller, Clayton L. Rumble

"A field net acid generation (NAG) test procedure has been utilized on-site to identify, classify and map potentially acid forming overburden at the PT Kaltim Prima Coal (K.PC) mining operation situated in the tropical equatorial region of East Kalimantan, Indonesia. The field procedure involves routine use of a calibrated, site specific NAG test (rapid oxidation test using hydrogen peroxide) which has a tum-around time of less than 24 hours and requires minimal sample preparation. It is used on geological drill-hole samples, for forward planning and overburden management; blast-hole samples, for day-to-day operational control and overburden scheduling; and final dump surface samples, for verification testing. This operational monitoring program has been in use at KPC for the past four years.Calibration and implementation of the field procedure has involved validating the NAG test using conventional acid-base accounting techniques, producing an overburden geochemical classification scheme, optimizing laboratory and sample preparation procedures, and ongoing quality management. This paper presents background theory and practical application in a case study format."

Jan 1, 1999

By S. F. Cheng

Among the many extraordinary features of the rare earths are their magnetic and magnetoelastic properties. The rare earths, e.g. Tb, Dy, Nd, Sm, are known worldwide for their large magnetocrystalline anisotropy and magnetization, which has led to the importance of magnetic rare earths as vital ingredients of modem permanent magnets. In this paper, we focus on the strain dependence of these giant effects which gives rise to huge magnetostrictions, magnetomechanical couplings, and ?E effects. Magnetostrictions greater than 10-3 have been measured at temperatures as high as 500 K. At low temperatures magnetostrictions reaches -1%. ?E effects - 10. No other solid state material has matched these values. A proper balance of magnetic anisotropy and magnetostriction, plus a proper choice of crystal axes lead to alloys which can switch large quantities of energy between the internal (magnetic) and external (mechanical) states with the application of small triggering magnetic fields. In addition to the traditional use of these materials in transduction, they are particularly valuable for smart systems where reliability and robustness are needed such as active structure stiffening and active vibration control.

Jan 1, 1997

By Olga Slavkina

A new technology of bacterial leaching by means of the Thiobacillus ferrooxidance bacteria is proposed. The equations of reactions that describe of the first and the second stage of bacterial leaching of sulfide raw materials containing non-ferrous metals are given. The theory is analyzed and the technology of processing of some complicated substandard concentrate containing copper and zinc is proposed. The main technological operations including a two-stage bacterial leaching and stages of copper and zinc recovery in the form of marketable product are described. The results of the experimental validation of the main technological parameters of the first stage are given. The main possibilities of a more complete zinc and copper recovery at the second stage of bacterial leaching are discussed in comparison with single-stage leaching process.

Jan 1, 2003

By R. M. Cunningham

Asarco operates one of the largest individual copper electrolytic refineries in the world at Amarillo, Texas. The feed for this refinery is a mixture of anodes produced at Asarco smelters and copper purchased t?om a number of primary and secondary sources. The variation in feed makes it imperative that the refinery practices state-of-the-art quality control to minimize the effects'of unwanted impurities in the electrolytic refining process. In late 1993, a plant designed to sigru6cantly reduce the antimony and bismuth levels in the electrolyte was commissioned. The purification plant uses ion exchange technology in conjunction with a novel strippiing system developed by Zeneca Specialties (U.K.). The strippiing system permits the recycling of the eluant and thus avoids the extremely high costs of stripping with conventional reagents. In addition, the environmental impact of treating the eluant for recovery of antimony and bismuth is minimized. This paper outlines the development of the technology and, in particular, describes the operational practices and improvements at Amarillo since the commissioning of the plant.

Jan 1, 1997

By K. A. Elbarawy

Processing of Egyptian barite ore with a composition of 85.5% BaSO4; 2.75%SiO2;1.56%Fe2O3 and 5.1% Al2O3 was performed with the aim to prepare pure barium salts. The process took place through pelletization-solid state reduction and leaching steps. Each of these steps was optimized. Pure barium sulphate (99% < 0.82µm) and carbonate (99%<0.75µm )were the final products. This article deals with the reduction process that occur whn coal was added to the ore during pelletization in the ratio of 5:1 stoichiometry. Optimum reduction of pellets of 8-12mm in diameter was achieved after 60 minutes at 1050oC and under a rate of 5 lmin-1 of nitrogen atmosphere, where 87.79% of the ore was reduced. The kinetic studies showed that the reduction process could be modeled according to the core mechanism of diffusion control in which the effective diffusivity is based on the surface area of unreacted ore. The activation energy calculated was 92.7 kJmol-1.

Jan 1, 2006